WO2014083603A1 - Method for producing 5-hydroxymethylfurfural using cellulose as raw material - Google Patents

Method for producing 5-hydroxymethylfurfural using cellulose as raw material Download PDF

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WO2014083603A1
WO2014083603A1 PCT/JP2012/080552 JP2012080552W WO2014083603A1 WO 2014083603 A1 WO2014083603 A1 WO 2014083603A1 JP 2012080552 W JP2012080552 W JP 2012080552W WO 2014083603 A1 WO2014083603 A1 WO 2014083603A1
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mixing
channel
fluid
cellulose
reaction
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PCT/JP2012/080552
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French (fr)
Japanese (ja)
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近藤　健之
上川　将行
松尾　俊明
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株式会社日立製作所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • the present invention relates to a method for producing 5-hydroxymethylfurfural using cellulose contained in biomass as a raw material and an apparatus used for the method.
  • 5-Hydroxymethylfurfural is a precursor of 2,5-dimethylfuran, which has potential as a biogasoline, and 2,5-furandicarboxylic acid, which can be an alternative to terephthalic acid, a raw material for plastics. Since it is a body and also a raw material for a sickle cell disease therapeutic agent, it has attracted attention as a useful compound. It is known that 5-HMF can be produced from monosaccharides (glucose and fructose). If 5-HMF can be efficiently produced from cellulose contained in biomass via monosaccharides, a new method for using biomass Can be provided.
  • Non-Patent Document 1 describes the decomposition behavior of cellulose in super / subcritical water, and 5-HMF is a by-product in the reaction to obtain monosaccharides and oligosaccharides by treating cellulose with super / subcritical water. It is described that about 10% at maximum was produced as a product. However, a method for obtaining 5-HMF in high yield from cellulose is not known.
  • 5-HMF is obtained by dehydration reaction of monosaccharides (glucose and fructose). Therefore, the production method of 5-HMF using biomass as a raw material, as represented by the following formula, mainly includes the first reaction of hydrolyzing cellulose contained in biomass to obtain glucose and the dehydration reaction of glucose. A second reaction to obtain 5-HMF.
  • an object of the present invention is to provide a method for producing 5-HMF from biomass at a high yield while suppressing the production of by-products, and an apparatus used for the method.
  • the method of the present invention is a method for continuously synthesizing 5-hydroxymethylfurfural using cellulose as a raw material, and the step of hydrolyzing cellulose by mixing cellulose and supercritical water or subcritical water was obtained.
  • a step of cooling and reducing the pressure of the reaction solution to a temperature and pressure for dehydration reaction of the monosaccharide, and mixing the acid heated to the dehydration reaction temperature of the monosaccharide ⁇ 100 ° C. and the reaction solution to dehydrate the monosaccharide It includes a step of performing a reaction to obtain 5-hydroxymethylfurfural.
  • the apparatus of the present invention is an apparatus for continuously producing 5-hydroxymethylfurfural, which is a super-subcritical water supply unit equipped with a pipe for feeding water, a water high-pressure pump, and a heater, and a cellulose slurry.
  • a monosaccharide dehydration reaction unit having a mixer for mixing the water, a subsequent pipe, a mixer for mixing cooling water into the fluid sent
  • hydrolysis of cellulose contained in biomass and dehydration reaction of monosaccharides obtained by the hydrolysis can be performed under conditions suitable for each reaction, resulting in high yield.
  • the method of the present invention comprises a step of hydrolyzing cellulose by mixing cellulose and supercritical water or subcritical water, and cooling and depressurizing the resulting reaction liquid to a temperature and pressure at which a monosaccharide is dehydrated. And a step of mixing the acid heated to the monosaccharide dehydration reaction temperature ⁇ 100 ° C. and the reaction solution to dehydrate the monosaccharide to obtain 5-HMF.
  • the hydrolysis of cellulose is preferably performed at 380 to 400 ° C. and 25 to 40 MPa, and the monosaccharide dehydration reaction is preferably performed at 200 to 280 ° C. and 10 to 20 MPa.
  • Monosaccharides obtained by hydrolysis of cellulose and convertible to 5-HMF include glucose and fructose produced by isomerization of glucose.
  • Cooling of the reaction liquid after hydrolysis of cellulose is preferably performed by directly mixing cooling water.
  • the method of the present invention further includes a step of stopping the dehydration reaction by cooling the reaction solution by directly mixing the cooling water with the reaction solution after the dehydration reaction of the monosaccharide.
  • mixing of cellulose and supercritical water or subcritical water mixing of cooling water after hydrolysis, mixing of acid and reaction solution, and mixing of cooling water after dehydration reaction, especially reaction with acid
  • the mixing of the liquid is preferably performed using a fluid mixer, referred to herein as a swirling mixer.
  • a fluid mixer referred to herein as a swirling mixer.
  • the hydrolysis reaction is once stopped, and then the monosaccharide obtained by hydrolysis is dehydrated.
  • the temperature and pressure suitable for hydrolysis of cellulose using super-subcritical water is higher than the temperature and pressure suitable for dehydration of monosaccharides. Therefore, after the hydrolysis, it is possible to realize conditions suitable for the dehydration reaction only by cooling and depressurization, and it is not necessary to reheat or repressurize the reaction solution. The operating cost does not increase compared with the conventional method.
  • An apparatus for continuously producing 5-HMF used in the method of the present invention is a super-subcritical water supply unit equipped with a pipe for feeding water, a water high-pressure pump, and a heater, and a cellulose slurry.
  • a cellulose slurry supply unit equipped with a pipe, a cellulose slurry high-pressure pump, and a heater, a mixer for mixing the fluid sent from the super-subcritical water supply unit and the cellulose slurry supply unit, and a subsequent pipe A cellulose hydrolysis reaction unit provided, a mixer for mixing cooling water with the fluid sent from the hydrolysis reaction unit, and a first cooling decompression unit equipped with a pressure reducing valve, and a fluid containing acid are fed.
  • a mixer for mixing an acid with a fluid fed from the first cooling pressure reducing unit having a pipe, an acid high-pressure pump for feeding a fluid containing acid, and an acid supply unit provided with a heater And a monosaccharide dehydration reaction section provided with a subsequent pipe, a mixer for mixing cooling water with the fluid sent from the monosaccharide dehydration reaction section, and a second cooling pressure reduction section provided with a pressure reducing valve.
  • At least one of the mixers is a swirl flow mixer described later.
  • the temperature and pressure in the pipe following the mixer in the cellulose hydrolysis reaction section are 380 to 400 ° C. and 25 to 40 MPa, and the temperature and pressure in the pipe following the mixer in the monosaccharide dehydration reaction section. Is preferably 200 to 280 ° C. and 10 to 20 MPa.
  • FIG. 1 is a schematic view showing an example of an apparatus used in the method for producing 5-HMF of the present invention.
  • cellulose slurry and super-subcritical water are mixed by a mixer, and then subjected to a hydrolysis reaction of cellulose in a subsequent pipe under high temperature and high pressure.
  • the reaction solution is cooled and depressurized by a cooler and a pressure reducing valve to a temperature and pressure suitable for the monosaccharide dehydration reaction while the hydrolysis reaction is stopped.
  • the reaction solution is further mixed with an acid by a mixer, and is subjected to a dehydration reaction of monosaccharides (glucose, fructose, etc.) obtained by hydrolysis of cellulose in the subsequent piping.
  • monosaccharides glucose, fructose, etc.
  • reaction solution is cooled and decompressed by a cooler and a pressure reducing valve, and a reaction product containing 5-HMF is recovered.
  • the apparatus becomes large and the indirect cooling by the cooler is not in time and the reaction time cannot be controlled, it is possible to adopt a configuration in which the cooling water is directly mixed with the reaction liquid instead of the cooler (see FIG. 2). .
  • FIG. 3 is a diagram showing a more specific configuration example of the 5-HMF manufacturing apparatus of the present invention.
  • the flow until the recovery of 5-HMF from cellulose derived from biomass will be described in detail.
  • water is fed at a water high pressure pump (0110) at an optimum hydrolysis reaction pressure of cellulose of 25 to 40 MPa, and supercritical or subcritical water preheater (0120) is used to achieve a supercritical or subcritical temperature. Raise the temperature.
  • cellulose slurry aqueous dispersion of cellulose
  • a cellulose slurry high-pressure pump (0210)
  • heated to 100 to 200 ° C. with a cellulose slurry preheater (0220).
  • both are mixed with super / subcritical water and a cellulose slurry mixer (0300), and the hydrolysis reaction of cellulose is started instantaneously at 380 to 400 ° C. and 25 to 40 MPa.
  • the hydrolysis reaction time is preferably 0.1 to 120 seconds, particularly 5 to 15 seconds.
  • FIG. 4 is a view showing an example of an apparatus for supplying cellulose slurry.
  • the supply flow rate of the cellulose slurry is preferably 2 m / s or more from the viewpoint of preventing precipitation of cellulose.
  • the concentration of cellulose in the slurry is preferably 1 to 30% by weight, particularly 5 to 10% by weight, considering the cost and the risk of pipe clogging due to a decrease in fluidity.
  • the reaction solution hydrolyzed in the hydrolysis reaction pipe (0350) is mixed with the cooling water fed by the first cooling water high-pressure pump (0410) by the first cooling water mixer (0500), and instantly a monosaccharide.
  • the reaction is cooled to a temperature suitable for the dehydration reaction, and the hydrolysis reaction is stopped.
  • the temperature of the reaction liquid after cooling is preferably 200 to 280 ° C., particularly preferably 230 to 250 ° C.
  • the cooled reaction liquid is depressurized to a pressure suitable for monosaccharide dehydration reaction by the first pressure reducing valve (0530).
  • the pressure of the reaction liquid after depressurization is preferably 10 to 20 MPa, particularly preferably 15 to 20 MPa (see the pressure and temperature ranges of hydrolysis and dehydration reactions in FIG. 5).
  • the fed dehydration reaction catalyst (acid) using the dehydration reaction catalyst supply pump (0610) is heated to a predetermined temperature by the dehydration reaction catalyst preheater (0620), and in the dehydration reaction catalyst and reaction liquid mixer (0700).
  • the dehydration reaction is started by mixing with the reaction solution.
  • the acid as the dehydration reaction catalyst is preferably sulfuric acid or phosphoric acid.
  • the amount of acid added is 1 to 5 mol equivalents, particularly 2 to 4 mol equivalents relative to the monosaccharides contained in the system, and the acid heating temperature is such as sulfuric acid or phosphoric acid.
  • the inorganic acid does not thermally decompose, it is preferable to set the temperature in the range of 140 to 340 ° C., particularly 210 to 270 ° C.
  • the heating temperature of the acid is preferably in the range of ⁇ 100 ° C., particularly ⁇ 40 ° C., with the temperature of the reaction solution to be mixed. By heating in advance before addition of the acid, it can be quickly and uniformly mixed with the reaction liquid when added to the reaction liquid, thereby suppressing the formation of by-products due to the non-uniformity of the reaction liquid. be able to.
  • the dehydration reaction time is preferably in the range of 5 seconds to 30 minutes, particularly 15 to 120 seconds.
  • the reaction solution is mixed with the cooling water fed from the second cooling water high-pressure pump (0810) and the second cooling water mixer (0900) after the optimal reaction time has elapsed. ) And the dehydration reaction is stopped.
  • the reaction solution is preferably cooled to a temperature of 50 ° C. or lower, particularly 30 ° C. or lower.
  • the carbon particles generated in a small amount by the monosaccharide dehydration reaction are captured by the carbon particle removal filter (1000) in the subsequent stage and separated and removed from the reaction solution. Thereafter, the pressure is reduced to the atmospheric pressure with the second pressure reducing valve (1200), and then recovered, and the hydroxyl group is esterified with acetic acid or the like and then purified by distillation to obtain 5-HMF.
  • 5-HMF can be converted to 2,5-furandicarboxylic acid, which is a substitute for terephthalic acid by oxidation treatment, and further converted to polyester by being polymerized with diols.
  • 5-HMF can be converted to 2,5-dimethylfuran, which is an alternative to biogasoline, by hydrogenation treatment.
  • the “swirl mixer” refers to a cylindrical mixing channel for mixing the first fluid and the second fluid, and a first fluid installed offset from the central axis of the mixing channel.
  • a plurality of first inlet channels and second inlet channels are alternately installed so as to rotate around the central axis of the mixing channel.
  • FIG. 6 shows a front view and a plan view of an example of a swirling mixer used as the super-subcritical water and cellulose slurry mixer (300) in the 5-HMF production apparatus of the present invention.
  • Other mixers can have the same configuration.
  • the end of the cylindrical mixing channel (320) is hermetically sealed, and the first inlet channel (310X) for guiding one fluid to the mixing channel (320) and the other end are sealed at the sealed end.
  • a second inlet channel (310Y) for guiding fluid to the mixing channel (320) is connected.
  • the first inlet channel (310X) and the second inlet channel (310Y) are connected to the mixing channel (320) in a state offset by ⁇ with respect to the central axis of the mixing channel (320).
  • a total of eight first inlet channels (310X) and second inlet channels (310Y) are alternately connected so as to rotate 45 ° around the central axis of the mixing channel (320). Since a plurality of the first and second inlet flow paths (310X, 310Y) are connected to the mixing flow path (320), a multilayer flow can be formed in the mixing flow path (320). Since the diffusion distance is reduced compared to the flow, the mixing property can be improved.
  • the first inlet channel (310X) and the second inlet channel (310Y) are connected at right angles to the central axis of the mixing channel (320), but the connection angle is It is not limited. By setting the connection angle to 90 ° or less, the flow direction in the mixing flow path (320) and the flow direction in the first and second inlet flow paths (310X, 310Y) are close to each other, so that pressure loss is reduced. Can increase production.
  • the first and second inlet channels (310X, 310Y) are described as having a rectangular cross section, but other shapes such as a cylindrical shape may be used.
  • the mixing channel (320) is assumed to have a cylindrical shape, but here, the cylindrical shape includes a case where the cross-section is a polygon approximate to a circle.
  • the flow rate QX of the raw material high-pressure pump (210) and the flow rate QY of the super / subcritical water high-pressure pump (110) are the same.
  • the first inlet channel (310X) and the second inlet are set so that the flow rates in the first inlet channel (310X) and the second inlet channel (310Y) are the same. Mixability can be improved by making the size of the flow path (310Y) different.
  • Is preferably set so as to satisfy the relationship of QX / SX QY / SY.
  • FIG. 7 shows an embodiment of a swirling mixer used in the 5-HMF manufacturing apparatus of the present invention.
  • a conical portion with low mixing property is generated on the central axis of the mixing flow path (320).
  • the mixability can be improved.
  • the distance between layers is further reduced, so that the mixing property can be improved.
  • the structure provided on the central axis of the mixing channel is preferably formed so as to become thinner (the cross-sectional area becomes smaller) toward the downstream.
  • Example 1 Using the apparatus described in FIG. 3, 5-HMF was continuously produced from cellulose.
  • a normal T-shaped mixer was used as the mixer.
  • Crystalline cellulose fine powder (Wako Pure Chemical Industries) was used as cellulose, and phosphoric acid (Wako Pure Chemical Industries) was used as a dehydration reaction catalyst.
  • the cellulose concentration of the cellulose slurry was 10% by weight.
  • the yield of 5-HMF was 50%. Moreover, even if the apparatus was operated continuously for 5 hours, piping clogging due to by-products did not occur.
  • FIG. 8 shows the change in reaction yield when the temperature before mixing the liquid obtained by cooling the hydrolysis reaction liquid of cellulose and phosphoric acid was changed. The temperature difference between them is adjusted by changing only the cooling water flow rate of the hydrolysis reaction solution and the flow rate / concentration of the phosphoric acid aqueous solution, and the reaction temperature of the hydrolysis reaction and the dehydration reaction temperature in the latter stage are the same as in Example 1.
  • a reaction test was conducted. As a result, when the temperature of the hydrolysis reaction solution of cellulose and the phosphoric acid aqueous solution were the same, the reaction yield was as high as 50%, but when both temperatures were changed by about 100 ° C., the reaction yield decreased to 40%.
  • Example 3 Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose.
  • FIG. 9 shows the change in reaction yield when the temperature of the hydrolysis reaction of cellulose is changed.
  • the temperature of the hydrolysis reaction was adjusted by changing the flow rate / temperature of the cellulose slurry and the supercritical water flow rate / temperature.
  • the temperature and pressure conditions for the dehydration reaction were the same as in the examples. As a result, the reaction yield peaked at a hydrolysis reaction temperature of 380 to 400 ° C., and was about 50%.
  • Example 4 Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose.
  • FIG. 10 shows the change in reaction yield when the hydrolysis pressure of cellulose is changed.
  • the hydrolysis reaction pressure was adjusted by changing the opening of the first pressure reducing valve.
  • the temperature and pressure conditions for the dehydration reaction were the same as in Example 1. As a result, the yield was high when the hydrolysis reaction pressure was 25 to 40 MPa.
  • FIG. 11 shows the change in the reaction yield when the dehydration temperature of the monosaccharide is changed.
  • the dehydration reaction temperature was adjusted by changing the cooling water flow rate of the hydrolysis reaction solution and the temperature of the phosphoric acid aqueous solution.
  • the reaction conditions for the hydrolysis reaction and the pressure for the dehydration reaction were the same as in Example 1.
  • the yield peaked at a dehydration reaction temperature of 240 ° C., and a high value of about 50% was observed at 230 to 250 ° C.
  • the temperature range in which a yield of 40% or more was obtained was 200 to 280 ° C.
  • Example 6 Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose.
  • FIG. 12 shows the change in the reaction yield when the dehydration reaction pressure of the monosaccharide is changed.
  • the dehydration reaction pressure was adjusted by changing the opening of the second pressure reducing valve.
  • the hydrolysis reaction conditions and the dehydration temperature conditions were the same as in Example 1. As a result, the yield was high at a dehydration reaction pressure of 15 to 20 MPa.
  • Example 7 Using the apparatus described in FIG. 3, 5-HMF was continuously produced from cellulose. Unlike Example 1, the swirl flow mixer shown in FIGS. 6 and 7 was used for the four mixers. Otherwise, the test was conducted under the same conditions as in Example 1. As a result, the yield of cellulose was 53%. Moreover, even if the apparatus was operated continuously for 5 hours, piping clogging due to by-products did not occur.
  • Example 2 (Comparative Example 2) Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. Example 1 was repeated except that phosphoric acid was mixed with the reaction solution at room temperature without heating in advance. The yield of 5-HMF remained at 35%, and further, the piping was blocked near the pressure reducing valve 60 minutes after the start of operation.

Abstract

The purpose of the present invention is to provide: a method for producing 5-hydroxymethylfurfural (5-HMF) from a biomass with high yield while preventing the production of any by-product; and an apparatus which can be used for the method. The present invention relates to a method for synthesizing 5-hydroxymethylfurfural continuously using a cellulose as a raw material, said method comprising the steps of: mixing the cellulose with supercritical water or subcritical water to hydrolyze the cellulose; cooling the resultant reaction solution and then reducing the pressure of the reaction solution to adjust the temperature and the pressure of the reaction solution to a temperature and a pressure both suitable for the dehydration reaction of a monosaccharide; and mixing an acid, which has been heated to a temperature that is up to 100˚C above or below the dehydration reaction temperature for the monosaccharide, with the reaction solution and then carrying out the dehydration reaction of the monosaccharide to produce 5-hydroxymethylfurfural.

Description

セルロースを原料とした５－ヒドロキシメチルフルフラールの製造方法Method for producing 5-hydroxymethylfurfural from cellulose
　本発明はバイオマスに含まれるセルロースを原料として５－ヒドロキシメチルフルフラールを製造する方法およびその方法に用いる装置に関する。 The present invention relates to a method for producing 5-hydroxymethylfurfural using cellulose contained in biomass as a raw material and an apparatus used for the method.
　５－ヒドロキシメチルフルフラール（５－ＨＭＦ）は、バイオガソリンとしての可能性を有する２，５－ジメチルフランや、プラスチックの原料であるテレフタル酸の代替物質になり得る２，５－フランジカルボン酸の前駆体であり、さらには鎌状赤血球症治療薬の原料ともなるため、有用な化合物として着目されている。５－ＨＭＦは単糖類（グルコースやフルクトース）から製造できることが知られており、バイオマスに含まれるセルロースから単糖類を経由して５－ＨＭＦを効率よく製造することができれば、バイオマスの新たな利用法を提供することが可能となる。 5-Hydroxymethylfurfural (5-HMF) is a precursor of 2,5-dimethylfuran, which has potential as a biogasoline, and 2,5-furandicarboxylic acid, which can be an alternative to terephthalic acid, a raw material for plastics. Since it is a body and also a raw material for a sickle cell disease therapeutic agent, it has attracted attention as a useful compound. It is known that 5-HMF can be produced from monosaccharides (glucose and fructose). If 5-HMF can be efficiently produced from cellulose contained in biomass via monosaccharides, a new method for using biomass Can be provided.
　非特許文献１には、超・亜臨界水中におけるセルロースの分解挙動について記載されており、セルロースを超・亜臨界水で処理して単糖類やオリゴ糖を得る反応において、５－ＨＭＦが副生成物として最大で１０％程度生成したことが記載されている。しかし、セルロースから５－ＨＭＦを高収率で得る方法は知られていない。 Non-Patent Document 1 describes the decomposition behavior of cellulose in super / subcritical water, and 5-HMF is a by-product in the reaction to obtain monosaccharides and oligosaccharides by treating cellulose with super / subcritical water. It is described that about 10% at maximum was produced as a product. However, a method for obtaining 5-HMF in high yield from cellulose is not known.
　５－ＨＭＦは単糖類（グルコースやフルクトース）の脱水反応により得られる。従って、バイオマスを原料とする５－ＨＭＦの製造方法は、下記の式で表されるように、主としてバイオマスに含まれるセルロースを加水分解してグルコースを得る第１の反応と、グルコースの脱水反応により５－ＨＭＦを得る第２の反応とからなる。
Figure JPOXMLDOC01-appb-C000001
 5-HMF is obtained by dehydration reaction of monosaccharides (glucose and fructose). Therefore, the production method of 5-HMF using biomass as a raw material, as represented by the following formula, mainly includes the first reaction of hydrolyzing cellulose contained in biomass to obtain glucose and the dehydration reaction of glucose. A second reaction to obtain 5-HMF.
Figure JPOXMLDOC01-appb-C000001
　しかし、そのような第１の加水分解と第２の脱水反応とは好ましい反応条件が大きく異なるため、それらの反応を同時に行おうとすれば、副生成物としてタールや炭素粒子などが生成してしまう。タールや炭素粒子などの副生成物の発生は、５－ＨＭＦの収率低下を招くと共に、製造装置における配管閉塞などの原因ともなり得るため好ましくない。そこで、本発明は、副生成物の生成を抑制しつつ、高収率でバイオマスから５－ＨＭＦを製造する方法およびその方法に用いる装置を提供することを目的とする。 However, since the preferable reaction conditions for the first hydrolysis and the second dehydration reaction are greatly different from each other, tar and carbon particles are generated as by-products if these reactions are performed simultaneously. . Generation of by-products such as tar and carbon particles is not preferable because it causes a decrease in the yield of 5-HMF and may cause piping blockage in the production apparatus. Accordingly, an object of the present invention is to provide a method for producing 5-HMF from biomass at a high yield while suppressing the production of by-products, and an apparatus used for the method.
　本発明者らは上述したような問題を検討した結果、セルロースの加水分解とそれに続く単糖類の脱水反応の反応条件を最適化し、バイオマスに含まれるセルロースから高収率で５－ＨＭＦを連続的に製造することを可能とする方法を見出した。 As a result of studying the problems as described above, the present inventors have optimized the reaction conditions of cellulose hydrolysis and subsequent monosaccharide dehydration reaction, and continuously produce 5-HMF from cellulose contained in biomass at a high yield. We have found a method that enables manufacturing.
　本発明の方法は、セルロースを原料として５－ヒドロキシメチルフルフラールを連続的に合成する方法であって、セルロースと超臨界水または亜臨界水とを混合してセルロースを加水分解する工程、得られた反応液を冷却および減圧して単糖類の脱水反応を行う温度および圧力にする工程、ならびに前記単糖類の脱水反応温度±１００℃に加熱した酸と前記反応液とを混合して単糖類の脱水反応を行い５－ヒドロキシメチルフルフラールを得る工程を含むことを特徴とする。 The method of the present invention is a method for continuously synthesizing 5-hydroxymethylfurfural using cellulose as a raw material, and the step of hydrolyzing cellulose by mixing cellulose and supercritical water or subcritical water was obtained. A step of cooling and reducing the pressure of the reaction solution to a temperature and pressure for dehydration reaction of the monosaccharide, and mixing the acid heated to the dehydration reaction temperature of the monosaccharide ± 100 ° C. and the reaction solution to dehydrate the monosaccharide It includes a step of performing a reaction to obtain 5-hydroxymethylfurfural.
　本発明の装置は、５－ヒドロキシメチルフルフラールを連続的に製造するための装置であって、水を送液する配管、水高圧ポンプ、およびヒーターを備えた超・亜臨界水供給部、セルローススラリーを送液する配管、セルローススラリー高圧ポンプ、およびヒーターを備えたセルローススラリー供給部、前記超・亜臨界水供給部と前記セルローススラリー供給部から送液された流体を混合するための混合器、およびそれに続く配管を備えたセルロース加水分解反応部、前記加水分解反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第１冷却減圧部、酸を含む流体を送液する配管、酸を含む流体を送液する酸高圧ポンプ、およびヒーターを備えた酸供給部を有し、前記第１冷却減圧部から送液された流体に酸を混合するための混合器、およびそれに続く配管を備えた単糖類脱水反応部、ならびに前記単糖類脱水反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第２冷却減圧部を備えることを特徴とする。 The apparatus of the present invention is an apparatus for continuously producing 5-hydroxymethylfurfural, which is a super-subcritical water supply unit equipped with a pipe for feeding water, a water high-pressure pump, and a heater, and a cellulose slurry. A cellulose slurry high-pressure pump and a cellulose slurry supply part equipped with a heater, a mixer for mixing the fluid sent from the super-subcritical water supply part and the cellulose slurry supply part, and Subsequent cellulose hydrolysis reaction section provided with piping, mixer for mixing cooling water into the fluid sent from the hydrolysis reaction section, and first cooling and decompression section equipped with a pressure reducing valve, fluid containing acid An acid supply unit equipped with a pipe for feeding a fluid, an acid high-pressure pump for feeding a fluid containing acid, and a heater, and the fluid fed from the first cooling pressure reducing unit A monosaccharide dehydration reaction unit having a mixer for mixing the water, a subsequent pipe, a mixer for mixing cooling water into the fluid sent from the monosaccharide dehydration reaction unit, and a pressure reducing valve And a second cooling decompression unit.
　本発明の方法によれば、バイオマスに含まれるセルロースの加水分解と、該加水分解により得られた単糖類の脱水反応とを、それぞれの反応に適した条件下で行うことができ、高収率で５－ＨＭＦを製造することができる。また、本発明の方法によれば、副生成物の生成を抑制して、配管やその他の機器の閉塞や摩耗を防ぎ、安定して５－ＨＭＦを製造することが可能となる。 According to the method of the present invention, hydrolysis of cellulose contained in biomass and dehydration reaction of monosaccharides obtained by the hydrolysis can be performed under conditions suitable for each reaction, resulting in high yield. Can produce 5-HMF. Further, according to the method of the present invention, it is possible to suppress the production of by-products, prevent clogging and wear of piping and other equipment, and stably produce 5-HMF.
本発明の５－ＨＭＦ製造方法に用いる装置の一例を示す概略図である。It is the schematic which shows an example of the apparatus used for the 5-HMF manufacturing method of this invention. 本発明の５－ＨＭＦ製造方法に用いる装置の他の一例を示す概略図である。It is the schematic which shows another example of the apparatus used for the 5-HMF manufacturing method of this invention. 本発明の５－ＨＭＦ製造方法に用いる装置の構成例を示す図である。It is a figure which shows the structural example of the apparatus used for the 5-HMF manufacturing method of this invention. セルローススラリーを供給するための装置の一例を示す図である。It is a figure which shows an example of the apparatus for supplying a cellulose slurry. 加水分解反応および脱水反応の圧力および温度範囲を表す相図である。It is a phase diagram showing the pressure and temperature range of a hydrolysis reaction and a dehydration reaction. 旋回流ミキサの一例の正面図および平面図である。It is the front view and top view of an example of a swirl flow mixer. 旋回流ミキサの一例の断面図である。It is sectional drawing of an example of a swirl flow mixer. ５－ＨＭＦ収率に及ぼす加水分解反応液と酸の温度差の影響を表すグラフである。It is a graph showing the influence of the temperature difference of a hydrolysis reaction liquid and an acid which has on 5-HMF yield. ５－ＨＭＦ収率に及ぼす加水分解反応温度の影響を表すグラフである。It is a graph showing the influence of the hydrolysis reaction temperature on 5-HMF yield. ５－ＨＭＦ収率に及ぼす加水分解反応圧力の影響を表すグラフである。It is a graph showing the influence of the hydrolysis reaction pressure on 5-HMF yield. ５－ＨＭＦ収率に及ぼす脱水反応温度の影響を表すグラフである。It is a graph showing the influence of the dehydration reaction temperature on 5-HMF yield. ５－ＨＭＦ収率に及ぼす脱水反応圧力の影響を表すグラフである。It is a graph showing the influence of the dehydration reaction pressure on 5-HMF yield. 比較例１で用いた従来の装置を示す概略図である。It is the schematic which shows the conventional apparatus used in the comparative example 1.
　本発明の方法は、セルロースと超臨界水または亜臨界水とを混合してセルロースを加水分解する工程、得られた反応液を冷却および減圧して単糖類の脱水反応を行う温度および圧力にする工程、ならびに前記単糖類の脱水反応温度±１００℃に加熱した酸と前記反応液とを混合して単糖類の脱水反応を行い５－ＨＭＦを得る工程を含む。セルロースの加水分解は３８０～４００℃、２５～４０ＭＰａで行い、単糖類の脱水反応を２００～２８０℃、１０～２０ＭＰａで行うことが好ましい。 The method of the present invention comprises a step of hydrolyzing cellulose by mixing cellulose and supercritical water or subcritical water, and cooling and depressurizing the resulting reaction liquid to a temperature and pressure at which a monosaccharide is dehydrated. And a step of mixing the acid heated to the monosaccharide dehydration reaction temperature ± 100 ° C. and the reaction solution to dehydrate the monosaccharide to obtain 5-HMF. The hydrolysis of cellulose is preferably performed at 380 to 400 ° C. and 25 to 40 MPa, and the monosaccharide dehydration reaction is preferably performed at 200 to 280 ° C. and 10 to 20 MPa.
　セルロースを加水分解して得られ、５－ＨＭＦに変換可能な単糖類としては、グルコースおよびグルコースが異性化して生じるフルクトースが挙げられる。 Monosaccharides obtained by hydrolysis of cellulose and convertible to 5-HMF include glucose and fructose produced by isomerization of glucose.
　単糖類の脱水反応において、脱水反応触媒である酸を予め脱水反応温度±１００℃に加熱すると、反応液に加えた際の酸が効率よく混合され、反応液に濃度や温度のムラが生じることを防ぐことができる。タールや炭素粒子などの副生成物は、反応液中に濃度や温度のムラが生じることにより発生すると考えられているため、酸を予め加熱することは副生成物の生成抑制に有利である。 In the dehydration reaction of monosaccharides, if the acid that is the catalyst for dehydration reaction is heated to the dehydration reaction temperature ± 100 ° C in advance, the acid when added to the reaction solution is efficiently mixed, resulting in uneven concentration and temperature in the reaction solution. Can be prevented. By-products such as tar and carbon particles are considered to be generated due to unevenness in concentration and temperature in the reaction solution, heating the acid in advance is advantageous for suppressing the formation of by-products.
　セルロースを加水分解した後の反応液の冷却は、冷却水を直接混合することにより行うことが好ましい。また、本発明の方法は、単糖類の脱水反応を行った後、冷却水を反応液に直接混合することにより反応液を冷却させて脱水反応を停止させる工程をさらに含むことが好ましい。 Cooling of the reaction liquid after hydrolysis of cellulose is preferably performed by directly mixing cooling water. Moreover, it is preferable that the method of the present invention further includes a step of stopping the dehydration reaction by cooling the reaction solution by directly mixing the cooling water with the reaction solution after the dehydration reaction of the monosaccharide.
　本発明の方法において、セルロースと超臨界水または亜臨界水との混合、加水分解後の冷却水の混合、酸と反応液の混合、および脱水反応後の冷却水の混合、中でも特に酸と反応液の混合は、本明細書で旋回流ミキサと称する流体混合器を用いて行うことが好ましい。旋回流ミキサを用いることにより、反応液に濃度や温度のムラが生じることを防ぐことができる。旋回流ミキサについては後に詳述する。 In the method of the present invention, mixing of cellulose and supercritical water or subcritical water, mixing of cooling water after hydrolysis, mixing of acid and reaction solution, and mixing of cooling water after dehydration reaction, especially reaction with acid The mixing of the liquid is preferably performed using a fluid mixer, referred to herein as a swirling mixer. By using the swirling mixer, it is possible to prevent the concentration and temperature of the reaction liquid from becoming uneven. The swirl mixer will be described in detail later.
　本発明の方法では、超・亜臨界水を用いてセルロースの加水分解を行った後、一度加水分解反応を停止させてから、加水分解で得られた単糖類の脱水反応を行う。このように、加水分解と脱水反応とを分けて行うことにより、それぞれの反応を最適な反応条件下で行うことが可能となる。また、一般に超・亜臨界水を用いてセルロースの加水分解に好適な温度・圧力は、単糖類の脱水反応に好適な温度・圧力よりも高い。従って、加水分解後は、冷却・減圧を行うのみで脱水反応に好適な条件を実現することができ、反応液の再加熱または再加圧を必要としないため、加水分解と脱水反応を同時に行う従来法と比較して運転コストが増大することもない。 In the method of the present invention, after hydrolysis of cellulose using super-subcritical water, the hydrolysis reaction is once stopped, and then the monosaccharide obtained by hydrolysis is dehydrated. Thus, by performing hydrolysis and dehydration reaction separately, it becomes possible to perform each reaction on optimal reaction conditions. In general, the temperature and pressure suitable for hydrolysis of cellulose using super-subcritical water is higher than the temperature and pressure suitable for dehydration of monosaccharides. Therefore, after the hydrolysis, it is possible to realize conditions suitable for the dehydration reaction only by cooling and depressurization, and it is not necessary to reheat or repressurize the reaction solution. The operating cost does not increase compared with the conventional method.
　本発明の方法に用いる５－ＨＭＦを連続的に製造するための装置は、水を送液する配管、水高圧ポンプ、およびヒーターを備えた超・亜臨界水供給部、セルローススラリーを送液する配管、セルローススラリー高圧ポンプ、およびヒーターを備えたセルローススラリー供給部、前記超・亜臨界水供給部と前記セルローススラリー供給部から送液された流体を混合するための混合器、およびそれに続く配管を備えたセルロース加水分解反応部、前記加水分解反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第１冷却減圧部、酸を含む流体を送液する配管、酸を含む流体を送液する酸高圧ポンプ、およびヒーターを備えた酸供給部を有し、前記第１冷却減圧部から送液された流体に酸を混合するための混合器、およびそれに続く配管を備えた単糖類脱水反応部、ならびに前記単糖類脱水反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第２冷却減圧部を備える。 An apparatus for continuously producing 5-HMF used in the method of the present invention is a super-subcritical water supply unit equipped with a pipe for feeding water, a water high-pressure pump, and a heater, and a cellulose slurry. A cellulose slurry supply unit equipped with a pipe, a cellulose slurry high-pressure pump, and a heater, a mixer for mixing the fluid sent from the super-subcritical water supply unit and the cellulose slurry supply unit, and a subsequent pipe A cellulose hydrolysis reaction unit provided, a mixer for mixing cooling water with the fluid sent from the hydrolysis reaction unit, and a first cooling decompression unit equipped with a pressure reducing valve, and a fluid containing acid are fed. A mixer for mixing an acid with a fluid fed from the first cooling pressure reducing unit, having a pipe, an acid high-pressure pump for feeding a fluid containing acid, and an acid supply unit provided with a heater And a monosaccharide dehydration reaction section provided with a subsequent pipe, a mixer for mixing cooling water with the fluid sent from the monosaccharide dehydration reaction section, and a second cooling pressure reduction section provided with a pressure reducing valve. .
　本発明の装置において、各混合器の少なくとも一つは後述する旋回流ミキサであることが好ましい。また、本発明の装置において、セルロース加水分解反応部における混合器に続く配管における温度および圧力は３８０～４００℃、２５～４０ＭＰａであり、単糖類脱水反応部における混合器に続く配管における温度および圧力は２００～２８０℃、１０～２０ＭＰａであることが好ましい。 In the apparatus of the present invention, it is preferable that at least one of the mixers is a swirl flow mixer described later. In the apparatus of the present invention, the temperature and pressure in the pipe following the mixer in the cellulose hydrolysis reaction section are 380 to 400 ° C. and 25 to 40 MPa, and the temperature and pressure in the pipe following the mixer in the monosaccharide dehydration reaction section. Is preferably 200 to 280 ° C. and 10 to 20 MPa.
　図１は、本発明の５－ＨＭＦの製造方法に用いる装置の一例を示す概略図である。まず、セルローススラリーと超・亜臨界水とがミキサにより混合され、その後段の配管中で、高温高圧下、セルロースの加水分解反応に供される。次いで、反応液は冷却器および減圧弁により、加水分解反応が停止され、かつ単糖類の脱水反応に好適である温度および圧力まで冷却・減圧される。反応液はさらにミキサにより酸と混合され、その後段の配管中で、セルロースの加水分解により得られた単糖類（グルコースやフルクトースなど）の脱水反応に供される。次いで反応液は冷却器および減圧弁により冷却・減圧され、５－ＨＭＦを含む反応生成物が回収される。なお、装置が大型化し、冷却器による間接冷却では間に合わず、反応時間を制御できない場合には、冷却器に代えて冷却水を反応液に直接混合する構成とすることもできる（図２参照）。 FIG. 1 is a schematic view showing an example of an apparatus used in the method for producing 5-HMF of the present invention. First, cellulose slurry and super-subcritical water are mixed by a mixer, and then subjected to a hydrolysis reaction of cellulose in a subsequent pipe under high temperature and high pressure. Next, the reaction solution is cooled and depressurized by a cooler and a pressure reducing valve to a temperature and pressure suitable for the monosaccharide dehydration reaction while the hydrolysis reaction is stopped. The reaction solution is further mixed with an acid by a mixer, and is subjected to a dehydration reaction of monosaccharides (glucose, fructose, etc.) obtained by hydrolysis of cellulose in the subsequent piping. Next, the reaction solution is cooled and decompressed by a cooler and a pressure reducing valve, and a reaction product containing 5-HMF is recovered. In addition, when the apparatus becomes large and the indirect cooling by the cooler is not in time and the reaction time cannot be controlled, it is possible to adopt a configuration in which the cooling water is directly mixed with the reaction liquid instead of the cooler (see FIG. 2). .
　図３は、本発明の５－ＨＭＦ製造装置のより具体的な構成例を示す図である。以下、図３を参照して、バイオマスに由来するセルロースから５－ＨＭＦを回収するまでの流れを詳細に説明する。 FIG. 3 is a diagram showing a more specific configuration example of the 5-HMF manufacturing apparatus of the present invention. Hereinafter, with reference to FIG. 3, the flow until the recovery of 5-HMF from cellulose derived from biomass will be described in detail.
　まず、水を水高圧ポンプ（０１１０）によりセルロースの最適加水分解反応圧力である２５～４０ＭＰａで送液し、超・亜臨界水プレヒーター（０１２０）で超臨界または亜臨界となる所定の温度に昇温する。一方、セルローススラリー（セルロースの水分散液）をセルローススラリー高圧ポンプ（０２１０）で２５～４０ＭＰａにて送液し、セルローススラリープレヒーター（０２２０）で１００～２００℃に昇温する。次いで、両者を超・亜臨界水およびセルローススラリーミキサ（０３００）で混合し、瞬時に３８０～４００℃、２５～４０ＭＰａにしてセルロースの加水分解反応を開始する。加水分解反応時間は０．１～１２０秒、特に５～１５秒とすることが好ましい。 First, water is fed at a water high pressure pump (0110) at an optimum hydrolysis reaction pressure of cellulose of 25 to 40 MPa, and supercritical or subcritical water preheater (0120) is used to achieve a supercritical or subcritical temperature. Raise the temperature. On the other hand, cellulose slurry (aqueous dispersion of cellulose) is fed at 25 to 40 MPa with a cellulose slurry high-pressure pump (0210), and heated to 100 to 200 ° C. with a cellulose slurry preheater (0220). Next, both are mixed with super / subcritical water and a cellulose slurry mixer (0300), and the hydrolysis reaction of cellulose is started instantaneously at 380 to 400 ° C. and 25 to 40 MPa. The hydrolysis reaction time is preferably 0.1 to 120 seconds, particularly 5 to 15 seconds.
　ここで、セルローススラリーを入れたタンク内では、十分に撹拌を行なうと共に、タンク外の循環ラインで循環送液を行い、セルローススラリーの沈殿を防止することが好ましい。図４はセルローススラリーを供給するための装置の一例を示す図である。セルローススラリーの供給流速は、セルロースの沈殿防止の観点から２ｍ／ｓ以上にすることが好ましい。スラリー中のセルロースの濃度は、コスト面や流動性低下による配管閉塞の恐れを考慮すると、１～３０重量％、特に５～１０重量％とすることが好ましい。 Here, in the tank containing the cellulose slurry, it is preferable to sufficiently agitate and circulate the solution in a circulation line outside the tank to prevent precipitation of the cellulose slurry. FIG. 4 is a view showing an example of an apparatus for supplying cellulose slurry. The supply flow rate of the cellulose slurry is preferably 2 m / s or more from the viewpoint of preventing precipitation of cellulose. The concentration of cellulose in the slurry is preferably 1 to 30% by weight, particularly 5 to 10% by weight, considering the cost and the risk of pipe clogging due to a decrease in fluidity.
　加水分解反応配管（０３５０）で加水分解された反応液は、第１冷却水高圧ポンプ（０４１０）により送液された冷却水と第１冷却水ミキサ（０５００）にて混合され、瞬時に単糖類の脱水反応に適した温度に冷却され、加水分解反応が停止される。冷却後の反応液の温度は２００～２８０℃、特に２３０～２５０℃の範囲の温度とすることが好ましい。冷却された反応液は、第１減圧弁（０５３０）で単糖類の脱水反応に適した圧力に減圧される。減圧後の反応液の圧力は１０～２０ＭＰａ、特に１５～２０ＭＰａの範囲の圧力とすることが好ましい（図５の加水分解反応および脱水反応の圧力および温度範囲を示す図を参照）。 The reaction solution hydrolyzed in the hydrolysis reaction pipe (0350) is mixed with the cooling water fed by the first cooling water high-pressure pump (0410) by the first cooling water mixer (0500), and instantly a monosaccharide. The reaction is cooled to a temperature suitable for the dehydration reaction, and the hydrolysis reaction is stopped. The temperature of the reaction liquid after cooling is preferably 200 to 280 ° C., particularly preferably 230 to 250 ° C. The cooled reaction liquid is depressurized to a pressure suitable for monosaccharide dehydration reaction by the first pressure reducing valve (0530). The pressure of the reaction liquid after depressurization is preferably 10 to 20 MPa, particularly preferably 15 to 20 MPa (see the pressure and temperature ranges of hydrolysis and dehydration reactions in FIG. 5).
　脱水反応触媒供給ポンプ（０６１０）を用いた送液された脱水反応触媒（酸）は、脱水反応触媒プレヒーター（０６２０）で所定の温度に加熱され、脱水反応触媒および反応液ミキサ（０７００）において反応液と混合され、脱水反応が開始される。脱水反応触媒としての酸は、硫酸、またはリン酸が好ましい。酸の添加量は、硫酸およびリン酸の場合は、系中に含まれる単糖類に対して１～５ｍｏｌ当量、特に２～４ｍｏｌ当量となる量、酸の加熱温度は、硫酸やリン酸などの無機酸は熱分解しないため、１４０～３４０℃、特に２１０～２７０℃の範囲の温度とすることが好ましい。酸の加熱温度は、混合される反応液の温度と±１００℃、特に±４０℃の範囲とすることが好ましい。酸を添加前に予め加熱しておくことにより、反応液に加えた際に反応液と速やかに均一に混合することができ、反応液の不均一性に起因する副生成物の生成を抑制することができる。脱水反応時間は、５秒～３０分、特に１５～１２０秒の範囲とすることが好ましい。 The fed dehydration reaction catalyst (acid) using the dehydration reaction catalyst supply pump (0610) is heated to a predetermined temperature by the dehydration reaction catalyst preheater (0620), and in the dehydration reaction catalyst and reaction liquid mixer (0700). The dehydration reaction is started by mixing with the reaction solution. The acid as the dehydration reaction catalyst is preferably sulfuric acid or phosphoric acid. In the case of sulfuric acid and phosphoric acid, the amount of acid added is 1 to 5 mol equivalents, particularly 2 to 4 mol equivalents relative to the monosaccharides contained in the system, and the acid heating temperature is such as sulfuric acid or phosphoric acid. Since the inorganic acid does not thermally decompose, it is preferable to set the temperature in the range of 140 to 340 ° C., particularly 210 to 270 ° C. The heating temperature of the acid is preferably in the range of ± 100 ° C., particularly ± 40 ° C., with the temperature of the reaction solution to be mixed. By heating in advance before addition of the acid, it can be quickly and uniformly mixed with the reaction liquid when added to the reaction liquid, thereby suppressing the formation of by-products due to the non-uniformity of the reaction liquid. be able to. The dehydration reaction time is preferably in the range of 5 seconds to 30 minutes, particularly 15 to 120 seconds.
　単糖類の脱水反応により発生した５－ＨＭＦは分解しやすいため、反応液は最適な反応時間経過後、第２冷却水高圧ポンプ（０８１０）から送液した冷却水と第２冷却水ミキサ（０９００）にて混合され、脱水反応が停止される。脱水反応を停止するため、反応液は５０℃以下、特に３０℃以下の温度に冷却することが好ましい。 Since 5-HMF generated by the dehydration reaction of monosaccharides is likely to be decomposed, the reaction solution is mixed with the cooling water fed from the second cooling water high-pressure pump (0810) and the second cooling water mixer (0900) after the optimal reaction time has elapsed. ) And the dehydration reaction is stopped. In order to stop the dehydration reaction, the reaction solution is preferably cooled to a temperature of 50 ° C. or lower, particularly 30 ° C. or lower.
　単糖類の脱水反応で微量発生した炭素粒子は後段の炭素粒子除去フィルター（１０００）にて捕捉され、反応液から分離除去される。この後、第２減圧弁（１２００）で大気圧に減圧された後に回収され、酢酸等で水酸基をエステル化した後に蒸留精製され、５－ＨＭＦが得られる。 The carbon particles generated in a small amount by the monosaccharide dehydration reaction are captured by the carbon particle removal filter (1000) in the subsequent stage and separated and removed from the reaction solution. Thereafter, the pressure is reduced to the atmospheric pressure with the second pressure reducing valve (1200), and then recovered, and the hydroxyl group is esterified with acetic acid or the like and then purified by distillation to obtain 5-HMF.
　５－ＨＭＦは、酸化処理によるテレフタル酸代替物質である２，５－フランジカルボン酸に変換することができ、さらにジオール類と重合されることによりポリエステルに変換することができる。また、５－ＨＭＦは水素添加処理することにより、バイオガソリンの代替物質である２，５－ジメチルフランに変換することができる。 5-HMF can be converted to 2,5-furandicarboxylic acid, which is a substitute for terephthalic acid by oxidation treatment, and further converted to polyester by being polymerized with diols. 5-HMF can be converted to 2,5-dimethylfuran, which is an alternative to biogasoline, by hydrogenation treatment.
　本発明の５－ＨＭＦ製造装置において、各ミキサ（０３００）（０５００）（０７００）（０９００）として旋回流ミキサを用いると、流体の混合性を改善し副生成物の生成を防止する観点から好ましい。ここで「旋回流ミキサ」とは、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、該混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、同様に混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、第１の入口流路と第２の入口流路とが混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合装置を意味する。 In the 5-HMF production apparatus of the present invention, when a swirling flow mixer is used as each mixer (0300) (0500) (0700) (0900), it is preferable from the viewpoint of improving fluid mixing properties and preventing the formation of by-products. . Here, the “swirl mixer” refers to a cylindrical mixing channel for mixing the first fluid and the second fluid, and a first fluid installed offset from the central axis of the mixing channel. A first inlet channel for flowing the fluid into the mixing channel, and a second inlet channel for flowing the second fluid into the mixing channel, similarly offset from the central axis of the mixing channel And a plurality of first inlet channels and second inlet channels are alternately installed so as to rotate around the central axis of the mixing channel.
　図６は、本発明の５－ＨＭＦ製造装置における超・亜臨界水およびセルローススラリーミキサ（３００）として用いる旋回流ミキサの一例の正面図および平面図を示したものである。なお、他のミキサについてもこれと同様の構成とすることができる。 FIG. 6 shows a front view and a plan view of an example of a swirling mixer used as the super-subcritical water and cellulose slurry mixer (300) in the 5-HMF production apparatus of the present invention. Other mixers can have the same configuration.
　円筒形状の混合流路（３２０）の端部は密閉されており、密閉された端部に一方の流体を混合流路（３２０）に導くための第１の入口流路（３１０Ｘ）と他方の流体を混合流路（３２０）に導くための第２の入口流路（３１０Ｙ）とが接続されている。第１の入口流路（３１０Ｘ）及び第２の入口流路（３１０Ｙ）は混合流路（３２０）の中心軸に対してδだけオフセットした状態で混合流路（３２０）と接続している。この構造により混合流路（３２０）内に旋回流を発生させ、混合性を改善することができる。 The end of the cylindrical mixing channel (320) is hermetically sealed, and the first inlet channel (310X) for guiding one fluid to the mixing channel (320) and the other end are sealed at the sealed end. A second inlet channel (310Y) for guiding fluid to the mixing channel (320) is connected. The first inlet channel (310X) and the second inlet channel (310Y) are connected to the mixing channel (320) in a state offset by δ with respect to the central axis of the mixing channel (320). With this structure, it is possible to generate a swirling flow in the mixing channel (320) and improve the mixing property.
　第１の入口流路（３１０Ｘ）と第２の入口流路（３１０Ｙ）は、混合流路（３２０）の中心軸の周りを４５°づつ回転するように交互に合計８本接続されている。第１及び第２の入口流路（３１０Ｘ、３１０Ｙ）が混合流路（３２０）に複数接続されているため、混合流路（３２０）内に多層流を形成することができ、従来の２層流に比べて拡散距離が低減されるため、混合性を改善することができる。 A total of eight first inlet channels (310X) and second inlet channels (310Y) are alternately connected so as to rotate 45 ° around the central axis of the mixing channel (320). Since a plurality of the first and second inlet flow paths (310X, 310Y) are connected to the mixing flow path (320), a multilayer flow can be formed in the mixing flow path (320). Since the diffusion distance is reduced compared to the flow, the mixing property can be improved.
　図６では、第１の入口流路（３１０Ｘ）及び第２の入口流路（３１０Ｙ）は、混合流路（３２０）の中心軸に対して直角に接続されているが、接続角度はこれに制限されるものではない。接続角度は９０°以下とすることで、混合流路（３２０）での流れ方向と第１及び第２の入口流路（３１０Ｘ、３１０Ｙ）での流れ方向とが近づくため、圧力損失を低減することができ、生産量を増大することができる。 In FIG. 6, the first inlet channel (310X) and the second inlet channel (310Y) are connected at right angles to the central axis of the mixing channel (320), but the connection angle is It is not limited. By setting the connection angle to 90 ° or less, the flow direction in the mixing flow path (320) and the flow direction in the first and second inlet flow paths (310X, 310Y) are close to each other, so that pressure loss is reduced. Can increase production.
　図６では、第１及び第２の入口流路（３１０Ｘ、３１０Ｙ）の断面は矩形状であるように記載しているが、円筒形状等の他の形状であっても構わない。また、混合流路（３２０）は円筒形状であるとしているが、ここで円筒形状には断面が円に近似される多角形である場合も含まれるものとする。第１及び第２の入口流路（３１０Ｘ、３１０Ｙ）の幅Ｗは、混合流路（３２０）の直径φの１／４にすることで最も高い混合性が得られる。 In FIG. 6, the first and second inlet channels (310X, 310Y) are described as having a rectangular cross section, but other shapes such as a cylindrical shape may be used. Further, the mixing channel (320) is assumed to have a cylindrical shape, but here, the cylindrical shape includes a case where the cross-section is a polygon approximate to a circle. By setting the width W of the first and second inlet channels (310X, 310Y) to ¼ of the diameter φ of the mixing channel (320), the highest mixing property can be obtained.
　また、混合流路（３２０）での混合性を高めるためには、原料高圧ポンプ（２１０）の流量ＱＸと超・亜臨界水高圧ポンプ（１１０）の流量ＱＹとが同一であることが望ましい。しかし、両者が異なる場合は、第１の入口流路（３１０Ｘ）と第２の入口流路（３１０Ｙ）における流速が同一になるように、第１の入口流路（３１０Ｘ）と第２の入口流路（３１０Ｙ）の寸法を異なるものにすることで混合性を改善することができる。すなわち、第１の入口流路（３１０Ｘ）の流量ＱＸ、及びＷ×ＨＸで求められる断面積ＳＸと、第２の入口流路（３１０Ｙ）の流量ＱＹ、及びＷ×ＨＹで求められる断面積ＳＹとが、ＱＸ／ＳＸ＝ＱＹ／ＳＹの関係を満足するように設定することが望ましい。 Also, in order to improve the mixing property in the mixing channel (320), it is desirable that the flow rate QX of the raw material high-pressure pump (210) and the flow rate QY of the super / subcritical water high-pressure pump (110) are the same. However, when they are different, the first inlet channel (310X) and the second inlet are set so that the flow rates in the first inlet channel (310X) and the second inlet channel (310Y) are the same. Mixability can be improved by making the size of the flow path (310Y) different. That is, the cross-sectional area SX determined by the flow rate QX and W × HX of the first inlet flow path (310X), and the cross-sectional area SY determined by the flow rate QY and W × HY of the second inlet flow path (310Y). Is preferably set so as to satisfy the relationship of QX / SX = QY / SY.
　図７に、本発明の５－ＨＭＦ製造装置に用いる旋回流ミキサの一実施形態を示す。旋回流を用いたミキサでは、混合流路（３２０）の中心軸上に円錐状の混合性の低い部分が発生する。この混合性の低い部分に構造物（３２５）を設けることで混合性を改善することができる。また、中心部分にそのような構造物が存在することにより、層間の距離がさらに低減されるため、混合性を改善することができる。混合流路の中心軸上に設ける構造物は、下流に向かうほど細くなる（断面積が小さくなる）ように形成することが好ましい。 FIG. 7 shows an embodiment of a swirling mixer used in the 5-HMF manufacturing apparatus of the present invention. In the mixer using the swirl flow, a conical portion with low mixing property is generated on the central axis of the mixing flow path (320). By providing the structure (325) in this low-mixability portion, the mixability can be improved. Moreover, since such a structure exists in the central portion, the distance between layers is further reduced, so that the mixing property can be improved. The structure provided on the central axis of the mixing channel is preferably formed so as to become thinner (the cross-sectional area becomes smaller) toward the downstream.
　以下、実施例を用いて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
（実施例１）
　図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。ミキサーには通常のＴ字型のミキサーを使用した。セルロースとして結晶性セルロース微粉末（和光純薬工業）を、脱水反応触媒としてリン酸（和光純薬工業）を用いた。セルローススラリーのセルロース濃度を１０重量％とした。４００℃、４０ＭＰａで１秒間加水分解反応させた後、冷却水を加えて２４０℃まで冷却させた。次いで、２４０℃に加熱したリン酸をグルコース換算で３ｍｏｌ当量添加し、１７ＭＰａで１２０秒間脱水反応させた。５－ＨＭＦの収率は５０％であった。また、装置を５時間連続して運転しても、副生成物による配管閉塞は生じなかった。 (Example 1)
Using the apparatus described in FIG. 3, 5-HMF was continuously produced from cellulose. A normal T-shaped mixer was used as the mixer. Crystalline cellulose fine powder (Wako Pure Chemical Industries) was used as cellulose, and phosphoric acid (Wako Pure Chemical Industries) was used as a dehydration reaction catalyst. The cellulose concentration of the cellulose slurry was 10% by weight. After a hydrolysis reaction at 400 ° C. and 40 MPa for 1 second, cooling water was added to cool to 240 ° C. Subsequently, 3 mol equivalent of phosphoric acid heated to 240 ° C. was added in terms of glucose, and dehydration was performed at 17 MPa for 120 seconds. The yield of 5-HMF was 50%. Moreover, even if the apparatus was operated continuously for 5 hours, piping clogging due to by-products did not occur.
（実施例２）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。セルロースの加水分解反応液を冷却した液とリン酸の混合前の温度を変えた時の反応収率の変化を図８に示す。両者の温度差は、加水分解反応液の冷却水流量およびリン酸水溶液の流量・濃度のみを変更して調整し、加水分解反応の反応温度、後段の脱水反応温度は実施例１と同一条件で反応試験を行った。その結果、セルロースの加水分解反応液とリン酸水溶液の温度が同じ場合、反応収率は５０％と高いが、両者温度が約１００℃変化すると反応収率が４０％まで低下した。 (Example 2)
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. FIG. 8 shows the change in reaction yield when the temperature before mixing the liquid obtained by cooling the hydrolysis reaction liquid of cellulose and phosphoric acid was changed. The temperature difference between them is adjusted by changing only the cooling water flow rate of the hydrolysis reaction solution and the flow rate / concentration of the phosphoric acid aqueous solution, and the reaction temperature of the hydrolysis reaction and the dehydration reaction temperature in the latter stage are the same as in Example 1. A reaction test was conducted. As a result, when the temperature of the hydrolysis reaction solution of cellulose and the phosphoric acid aqueous solution were the same, the reaction yield was as high as 50%, but when both temperatures were changed by about 100 ° C., the reaction yield decreased to 40%.
（実施例３）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。セルロースの加水分解反応の温度を変えた時の反応収率の変化を図９に示す。加水分解反応の温度は、セルローススラリーの流量・温度、超臨界水流量・温度を変更して調整した。また、脱水反応の温度・圧力条件は実施例と同一で実施した。その結果、反応収率は、加水分解反応温度が３８０～４００℃でピークとなり、５０％程度であった。 (Example 3)
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. FIG. 9 shows the change in reaction yield when the temperature of the hydrolysis reaction of cellulose is changed. The temperature of the hydrolysis reaction was adjusted by changing the flow rate / temperature of the cellulose slurry and the supercritical water flow rate / temperature. The temperature and pressure conditions for the dehydration reaction were the same as in the examples. As a result, the reaction yield peaked at a hydrolysis reaction temperature of 380 to 400 ° C., and was about 50%.
（実施例４）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。セルロースの加水分解圧力を変えた時の反応収率の変化を図１０に示す。加水分解反応圧力は第一減圧弁の開度を変更して調節した。また、脱水反応の温度・圧力条件は実施例１と同一で実施した。その結果、収率は加水分解反応圧力が２５～４０ＭＰａで高い値を示した。 Example 4
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. FIG. 10 shows the change in reaction yield when the hydrolysis pressure of cellulose is changed. The hydrolysis reaction pressure was adjusted by changing the opening of the first pressure reducing valve. The temperature and pressure conditions for the dehydration reaction were the same as in Example 1. As a result, the yield was high when the hydrolysis reaction pressure was 25 to 40 MPa.
（実施例５）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。単糖類の脱水反応温度を変えた時の反応収率の変化を図１１に示す。脱水反応温度は加水分解反応液の冷却水流量とリン酸水溶液の温度を変更することで調整した。また、加水分解反応の反応条件および脱水反応の圧力は実施例１と同一で実施した。その結果、収率は、脱水反応温度が２４０℃でピークとなり、２３０～２５０℃では約５０％の高い値を示した。また４０％以上の収率が得られる温度範囲は２００～２８０℃であった。 (Example 5)
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. FIG. 11 shows the change in the reaction yield when the dehydration temperature of the monosaccharide is changed. The dehydration reaction temperature was adjusted by changing the cooling water flow rate of the hydrolysis reaction solution and the temperature of the phosphoric acid aqueous solution. The reaction conditions for the hydrolysis reaction and the pressure for the dehydration reaction were the same as in Example 1. As a result, the yield peaked at a dehydration reaction temperature of 240 ° C., and a high value of about 50% was observed at 230 to 250 ° C. The temperature range in which a yield of 40% or more was obtained was 200 to 280 ° C.
（実施例６）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。単糖類の脱水反応圧力を変えた時の反応収率の変化を図１２に示す。脱水反応圧力は第二減圧弁の開度を変更して調節した。また、加水分解の反応条件、脱水反応の温度条件は実施例１同一で実施した。その結果、収率は脱水反応圧力が１５～２０ＭＰａで高い値を示した。 (Example 6)
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. FIG. 12 shows the change in the reaction yield when the dehydration reaction pressure of the monosaccharide is changed. The dehydration reaction pressure was adjusted by changing the opening of the second pressure reducing valve. The hydrolysis reaction conditions and the dehydration temperature conditions were the same as in Example 1. As a result, the yield was high at a dehydration reaction pressure of 15 to 20 MPa.
（実施例７）
　図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。実施例１と異なり、４つのミキサーには図６および図７に示す旋回流ミキサーを使用した。それ以外は実施例１と同一条件で試験を行った結果、セルロースの収率は５３％であった。また、装置を５時間連続して運転しても、副生成物による配管閉塞は生じなかった。 (Example 7)
Using the apparatus described in FIG. 3, 5-HMF was continuously produced from cellulose. Unlike Example 1, the swirl flow mixer shown in FIGS. 6 and 7 was used for the four mixers. Otherwise, the test was conducted under the same conditions as in Example 1. As a result, the yield of cellulose was 53%. Moreover, even if the apparatus was operated continuously for 5 hours, piping clogging due to by-products did not occur.
（比較例１）
　図１３に示したような、セルロースと酸と超・亜臨界水を同時に反応させる従来の装置を用いて５－ＨＭＦの連続的製造を試みた。原料と脱水反応触媒は実施例１と同一品を同一の比率で用いた。２４０℃、１５ＭＰａで１２０秒間反応させたところ、５－ＨＭＦの収率は２０％に留まった。また、運転開始５分経過後に減圧弁近傍で配管の閉塞が生じた。 (Comparative Example 1)
An attempt was made to continuously produce 5-HMF using a conventional apparatus for simultaneously reacting cellulose, acid, and super-subcritical water as shown in FIG. The same raw material and dehydration reaction catalyst as in Example 1 were used in the same ratio. When the reaction was carried out at 240 ° C. and 15 MPa for 120 seconds, the yield of 5-HMF remained at 20%. In addition, the piping was blocked near the pressure reducing valve after 5 minutes from the start of operation.
（比較例２）
　実施例１と同じ図３に記載した装置を用いて、セルロースから５－ＨＭＦを連続的に製造した。リン酸を予め加熱せずに室温で反応液に混合した以外は実施例１と同様にした。５－ＨＭＦの収率は３５％に留まり、さらに運転開始６０分経過後に減圧弁近傍で配管の閉塞が生じた。 (Comparative Example 2)
Using the same apparatus described in FIG. 3 as in Example 1, 5-HMF was continuously produced from cellulose. Example 1 was repeated except that phosphoric acid was mixed with the reaction solution at room temperature without heating in advance. The yield of 5-HMF remained at 35%, and further, the piping was blocked near the pressure reducing valve 60 minutes after the start of operation.
　本明細書中で引用した全ての刊行物、特許および特許出願をそのまま参考として本明細書中にとり入れるものとする。 All publications, patents and patent applications cited in this specification shall be incorporated into this specification as they are.
０１００　…　水ヘッダー
０１１０　…　水高圧ポンプ
０１２０　…　超・亜臨界水プレヒーター
０１５０　…　超・亜臨界水供給配管
０２００　…　セルローススラリーヘッダー
０２１０　…　セルローススラリー高圧ポンプ
０２２０　…　セルローススラリープレヒーター
０２５０　…　セルローススラリー供給配管
０３００　…　超・亜臨界水およびセルローススラリーミキサ
０３５０　…　加水分解反応配管
０４００　…　第１冷却水ヘッダー
０４１０　…　第１冷却水高圧ポンプ
０４５０　…　第１冷却水供給配管
０５００　…　第１冷却水ミキサ
０５３０　…　第１減圧弁
０５５０　…　第１冷却水混合配管
０６００　…　脱水反応触媒供給ヘッダー
０６１０　…　脱水反応触媒高圧ポンプ
０６２０　…　脱水反応触媒プレヒーター
０６５０　…　脱水反応触媒供給配管
０７００　…　脱水反応触媒および反応液ミキサ
０７５０　…　脱水反応配管
０８００　…　第２冷却水ヘッダー
０８１０　…　第２冷却水高圧ポンプ
０８５０　…　第２冷却水供給配管
０９００　…　第２冷却水ミキサ
０９３０　…　弁
０９５０　…　第２冷却水混合配管
１０００　…　炭素粒子除去フィルタ
１０３０　…　弁
１０３０　…　反応液ライン
１０９０　…　ドレン
１１００　…　逆洗流体供給ヘッダー
１１１０　…　逆洗流体供給ポンプ
１１３０　…　弁
１１５０　…　逆洗流体供給配管
１１６０　…　逆洗流体分岐
１１７０　…　弁
１２００　…　第２減圧弁
１２５０　…　減圧配管
１３５０　…　反応液排出配管
１３９０　…　反応液排出配口 0100 ... Water header 0110 ... Water high pressure pump 0120 ... Super / subcritical water preheater 0150 ... Super / subcritical water supply pipe 0200 ... Cellulose slurry header 0210 ... Cellulose slurry high pressure pump 0220 ... Cellulose slurry preheater 0250 ... Cellulose slurry supply pipe 0300 ... Super-subcritical water and cellulose slurry mixer 0350 ... Hydrolysis reaction pipe 0400 ... First cooling water header 0410 ... First cooling water high-pressure pump 0450 ... First cooling water supply pipe 0500 ... First cooling water mixer 0530 ... First 1 pressure reducing valve 0550 ... first cooling water mixing pipe 0600 ... dehydration reaction catalyst supply header 0610 ... dehydration reaction catalyst high pressure pump 0620 ... dehydration reaction catalyst preheater 0650 ... dehydration reaction catalyst supply pipe 0700 ... dehydration Reaction catalyst and reaction liquid mixer 0750 ... dehydration reaction pipe 0800 ... second cooling water header 0810 ... second cooling water high-pressure pump 0850 ... second cooling water supply pipe 0900 ... second cooling water mixer 0930 ... valve 0950 ... second cooling water Mixing pipe 1000 ... Carbon particle removal filter 1030 ... Valve 1030 ... Reaction liquid line 1090 ... Drain 1100 ... Backwash fluid supply header 1110 ... Backwash fluid supply pump 1130 ... Valve 1150 ... Backwash fluid supply pipe 1160 ... Backwash fluid branch 1170 ... Valve 1200 ... Second pressure reducing valve 1250 ... Pressure reducing pipe 1350 ... Reaction liquid discharge pipe 1390 ... Reaction liquid discharge port

Claims (9)

  1. 　セルロースを原料として５－ヒドロキシメチルフルフラールを連続的に合成する方法であって、セルロースと超臨界水または亜臨界水とを混合してセルロースを加水分解する工程、得られた反応液を冷却および減圧して単糖類の脱水反応を行う温度および圧力にする工程、ならびに前記単糖類の脱水反応温度±１００℃に加熱した酸と前記反応液とを混合して単糖類の脱水反応を行い５－ヒドロキシメチルフルフラールを得る工程を含む、前記方法。 A method of continuously synthesizing 5-hydroxymethylfurfural using cellulose as a raw material, a process of hydrolyzing cellulose by mixing cellulose and supercritical water or subcritical water, cooling and depressurizing the resulting reaction liquid And a step of bringing the monosaccharide to a dehydration reaction at a temperature and pressure, and mixing the acid heated to the monosaccharide dehydration reaction temperature ± 100 ° C. and the reaction solution to conduct a monosaccharide dehydration reaction to give 5-hydroxy Said method comprising the step of obtaining methylfurfural.
  2. 　セルロースの加水分解を３８０～４００℃、２５～４０ＭＰａで行い、単糖類の脱水反応を２００～２８０℃、１０～２０ＭＰａで行う、請求項１に記載の方法。 2. The method according to claim 1, wherein cellulose is hydrolyzed at 380 to 400 ° C. and 25 to 40 MPa, and monosaccharide dehydration is performed at 200 to 280 ° C. and 10 to 20 MPa.
  3. 　酸と反応液の混合を、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、前記混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、前記混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、前記第１の入口流路と前記第２の入口流路とが前記混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合器を用いて行う、請求項１または２に記載の方法。 A cylindrical mixing channel for mixing the acid and the reaction liquid to mix the first fluid and the second fluid, and the first fluid that is installed offset from the central axis of the mixing channel A first inlet flow channel for flowing into the flow channel, and a second inlet flow channel installed offset from the central axis of the mixing flow channel for flowing a second fluid into the mixing flow channel The first inlet channel and the second inlet channel are performed using a fluid mixer in which a plurality of the first inlet channel and the second inlet channel are alternately arranged so as to rotate around a central axis of the mixing channel. Or the method of 2.
  4. 　セルロースと超臨界水または亜臨界水との混合を、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、前記混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、前記混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、前記第１の入口流路と前記第２の入口流路とが前記混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合器を用いて行う、請求項１または２に記載の方法。 A mixture of cellulose and supercritical water or subcritical water is installed with a cylindrical mixing channel for mixing the first fluid and the second fluid, and offset from the central axis of the mixing channel. A first inlet channel for flowing the first fluid into the mixing channel, and a second inlet for flowing the second fluid into the mixing channel installed offset from the central axis of the mixing channel And a fluid mixer in which a plurality of the first inlet channel and the second inlet channel are alternately installed so as to rotate around a central axis of the mixing channel. The method according to claim 1, wherein the method is performed.
  5. 　セルロースの加水分解後の冷却を、冷却水を反応液に直接混合することにより行い、前記混合は、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、前記混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、前記混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、前記第１の入口流路と前記第２の入口流路とが前記混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合器を用いて行う、請求項１または２に記載の方法。 Cooling after hydrolysis of cellulose is performed by directly mixing cooling water with the reaction liquid, and the mixing is performed by mixing the first fluid and the second fluid with a cylindrical mixing channel, A first inlet channel installed to be offset from the central axis of the mixing channel and the first fluid to flow into the mixing channel, and a second fluid installed offset from the central axis of the mixing channel A second inlet channel for flowing into the mixing channel, so that the first inlet channel and the second inlet channel rotate around the central axis of the mixing channel The method according to claim 1, wherein the method is performed using a plurality of fluid mixers arranged alternately.
  6. 　単糖類の脱水反応を行った後、冷却水を反応液に直接混合することにより反応液を冷却させて脱水反応を停止させる工程をさらに含み、前記混合は、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、前記混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、前記混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、前記第１の入口流路と前記第２の入口流路とが前記混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合器を用いて行う、請求項１または２に記載の方法。 After the dehydration reaction of the monosaccharide, the method further includes a step of cooling the reaction liquid by directly mixing cooling water into the reaction liquid to stop the dehydration reaction, and the mixing includes the first fluid and the second fluid. And a first inlet channel for flowing a first fluid into the mixing channel installed offset from a central axis of the mixing channel, and the mixing A second inlet channel that is installed offset from the central axis of the channel and allows the second fluid to flow into the mixing channel, the first inlet channel and the second inlet channel The method according to claim 1, wherein a plurality of fluid mixers are alternately arranged so as to rotate around a central axis of the mixing flow path.
  7. 　水を送液する配管、水高圧ポンプ、およびヒーターを備えた超・亜臨界水供給部、
    　セルローススラリーを送液する配管、セルローススラリー高圧ポンプ、およびヒーターを備えたセルローススラリー供給部、
    　前記超・亜臨界水供給部と前記セルローススラリー供給部から送液された流体を混合するための混合器、およびそれに続く配管を備えたセルロース加水分解反応部、
    　前記加水分解反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第１冷却減圧部、
    　酸を含む流体を送液する配管、酸を含む流体を送液する酸高圧ポンプ、およびヒーターを備えた酸供給部を有し、前記第１冷却減圧部から送液された流体に酸を混合するための混合器、およびそれに続く配管を備えた単糖類脱水反応部、ならびに
    　前記単糖類脱水反応部から送液された流体に冷却水を混合するための混合器、および減圧弁を備えた第２冷却減圧部
    を備えた、５－ヒドロキシメチルフルフラールを連続的に製造するための装置。     Super-subcritical water supply unit equipped with piping for feeding water, high-pressure water pump, and heater,
    A cellulose slurry supply unit equipped with a pipe for feeding the cellulose slurry, a cellulose slurry high-pressure pump, and a heater,
    A cellulose hydrolyzing reaction section comprising a mixer for mixing the fluid sent from the super-subcritical water supply section and the cellulose slurry supply section, and a pipe following the mixer;
    A mixer for mixing cooling water with the fluid sent from the hydrolysis reaction section, and a first cooling pressure reducing section having a pressure reducing valve;
    A pipe for feeding a fluid containing an acid, an acid high-pressure pump for feeding a fluid containing an acid, and an acid supply unit equipped with a heater, and mixing the acid with the fluid fed from the first cooling pressure reducing unit And a monosaccharide dehydration reaction part provided with a subsequent pipe, a mixer for mixing cooling water with the fluid sent from the monosaccharide dehydration reaction part, and a pressure reducing valve. An apparatus for continuously producing 5-hydroxymethylfurfural having a two-cooling decompression unit.
  8. 　前記混合器の少なくとも一つが、第１の流体と第２の流体とを混合するための円筒形状の混合流路と、前記混合流路の中心軸からオフセットして設置され第１の流体を混合流路に流入するための第１の入口流路と、前記混合流路の中心軸からオフセットして設置され第２の流体を混合流路に流入するための第２の入口流路とを備え、前記第１の入口流路と前記第２の入口流路とが前記混合流路の中心軸の周りを回転するように交互に複数設置されている流体混合器である、請求項７に記載の装置。 At least one of the mixers is installed in a cylindrical mixing channel for mixing the first fluid and the second fluid and offset from the central axis of the mixing channel to mix the first fluid A first inlet flow channel for flowing into the flow channel, and a second inlet flow channel installed offset from the central axis of the mixing flow channel for flowing a second fluid into the mixing flow channel The fluid mixer in which a plurality of the first inlet channel and the second inlet channel are alternately installed so as to rotate around a central axis of the mixing channel. Equipment.
  9. 　前記セルロース加水分解反応部において、混合器に続く配管における温度および圧力が３８０～４００℃、２５～４０ＭＰａであり、前記単糖類脱水反応部において、混合器に続く配管における温度および圧力が２２０～２８０、１０～２０ＭＰａである、請求項７または８に記載の装置。 In the cellulose hydrolysis reaction part, the temperature and pressure in the pipe following the mixer are 380 to 400 ° C. and 25 to 40 MPa, and in the monosaccharide dehydration reaction part, the temperature and pressure in the pipe following the mixer are 220 to 280. The apparatus according to claim 7 or 8, wherein the pressure is 10 to 20 MPa.
PCT/JP2012/080552 2012-11-27 2012-11-27 Method for producing 5-hydroxymethylfurfural using cellulose as raw material WO2014083603A1 (en)

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